CN109836440A - A kind of preparation method of lithium diisopropylamine - Google Patents
A kind of preparation method of lithium diisopropylamine Download PDFInfo
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- CN109836440A CN109836440A CN201711198198.9A CN201711198198A CN109836440A CN 109836440 A CN109836440 A CN 109836440A CN 201711198198 A CN201711198198 A CN 201711198198A CN 109836440 A CN109836440 A CN 109836440A
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Abstract
The invention belongs to chemical intermediate preparation fields, and in particular to a kind of preparation method of lithium diisopropylamine.The synthetic method step 1: reaction kettle is cleaned up, and inert gas replacement three times, sequentially adds raw material, solvent, lithium metal；Step 2: reaction mixture is warming up to 25-60 DEG C；Step 3: maintaining 25-60 DEG C of reacting liquid temperature, into step 2 gained mixture, the solution of isoprene or styrene is added dropwise；Step 4: after being added dropwise, after the reaction was continued 0.5-2 hours, circulating water cooling, natural subsidence, supernatant is the corresponding solution of LDA.The present invention in order to solve the disadvantage in existing method, provide it is a kind of simply directly reacted at lithium metal, 25-60 DEG C, without the preparation process for the LDA that gas generates, reaction solvent for use can select according to actual needs.
Description
Technical field
The invention belongs to chemical intermediate preparation fields, and in particular to a kind of preparation method of lithium diisopropylamine.
Background technique
Lithium diisopropylamine (Lithium Diisopropylamide) abbreviation LDA, during being organic chemical synthesis
Common big steric hindrance, non-nucleophilic organic alkali.LDA is as an organic alkali, PKa=36 in tetrahydrofuran, is widely applied
It is formed in the unit processes such as carbanion, halogen-lithium exchange in alfa- enolizations of aldehyde ketone, deprotonation.
The most classic synthetic method of lithium diisopropylamine is that butyl lithium hexane solution is slowly added dropwise to two under low temperature
It is obtained in the tetrahydrofuran solution of isopropylamine.General reaction temperature is subzero 78 degree to subzero 25 degree, and uses fourth
Base lithium, than relatively hazardous.Further, since commercially available butyl lithium is generally hexane solution, major concentration has 1.0-2.5M, from fourth
The LDA of base lithium preparation inevitably introduces n-hexane, if reaction system is not intended to introduce n-hexane, which can not expire
Foot.
During butyl lithium is added dropwise, amount of heat is released in reaction, so needing to maintain low temperature always, so energy consumption
Relatively high, during preparing LDA, butyl lithium used generates the imflammable gas of equimolar amounts, positive fourth after reacting with diisopropylamine
Alkane.If needing first to prepare butyl lithium from lithium, then obtaining LDA again.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation process of lithium diisopropylamine, the present invention is in order to solve existing side
Disadvantage in method, provide it is a kind of simply directly reacted at lithium metal, 25-60 DEG C, without gas generate LDA system
Standby technique, reaction solvent for use can select according to actual needs.
To achieve the goals above, the present invention adopts the following technical scheme:
A method of preparing lithium diisopropylamine, the preparation method the following steps are included:
Step 1: reaction kettle being cleaned up, inert gas replacement three times, sequentially adds raw material, solvent for use, lithium metal；
Step 2: reaction mixture is warming up to 25-60 DEG C；
Step 3: maintaining 25-60 DEG C of reacting liquid temperature, into step 2 gained mixture, the molten of isoprene or styrene is added dropwise
Liquid starts that a small amount of initiation reaction is added dropwise, and maintains temperature of reaction system after initiation by adjusting rate of addition and circulating water velocity,
It prevents from temperature from crossing high product to degenerate.
Step 4: after being added dropwise, after the reaction was continued 0.5-2 hours, circulating water cooling, natural subsidence, supernatant is
The corresponding solution of LDA.
Preferably, raw materials used in the preparation method step 2 is n-hexane, normal heptane, tetrahydrofuran, methyl tertbutyl
Ether, ether, disopropyl ethyl amine or dimethylethyl amine.
Preferably, the temperature in the preparation method step 2 is 35-40 DEG C.
Preferably, the maintenance temperature in the preparation method step 3 is 35-40 DEG C.
Preferably, the solution solvent of isoprene or styrene is methyl tertiary butyl ether(MTBE) or four in the preparation method step 3
Hydrogen furans.
Compared with prior art, effect of the invention is that: the present invention not only reduces cost, protects environment, and
And easy to operate, convenient post-treatment, high income, synthesis is simple, is suitble to industrialized production.
Specific embodiment
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Embodiment 1
The present invention is further explained in the light of specific embodiments.
The preparation of one: 2.0MLDATHF/ hexane solution of embodiment
Under inert gas shielding, by 355 grams of n-hexanes, 12.4 grams of tetrahydrofurans, 13.9 grams of lithiums are placed in 2L there-necked flask, and reaction is mixed
It closes object and is warming up to 30-35 degree, 112 grams of tetrahydrofuran solutions of 69.5 grams of isoprene are added dropwise, maintain reaction solution during being added dropwise
Temperature is no more than 40 degree.Stop stirring after reacting half an hour after being added dropwise, water-bath is cooled to 5-25 degree natural subsidence.
After sedimentation, supernatant inspection is packed after qualified.
The preparation of two: 2.0MLDATHF/ n-heptane solution of embodiment
Under inert gas shielding, by 368 grams of normal heptanes, 12.4 grams of tetrahydrofurans, 13.9 grams of lithiums are placed in 2L there-necked flask, and reaction is mixed
It closes object and is warming up to 30-35 degree, 112 grams of tetrahydrofuran solutions of 69.5 grams of isoprene are added dropwise, maintain reaction solution during being added dropwise
Temperature is no more than 40 degree.Stop stirring after reacting half an hour after being added dropwise, water-bath is cooled to 5-25 degree natural subsidence.
After sedimentation, supernatant inspection is packed after qualified.
The preparation of three: 2.0MLDATHF/ n-hexane of embodiment/ethylbenzene solution
Under inert gas shielding, by 355 grams of n-hexanes, 12.4 grams of tetrahydrofurans, 13.9 grams of lithiums are placed in 2L there-necked flask, and reaction is mixed
It closes object and is warming up to 30-35 degree, 112 grams of tetrahydrofuran solutions of 104.5 grams of styrene are added dropwise, maintain reaction solution temperature during being added dropwise
Degree is no more than 40 degree.Stop stirring after reacting half an hour after being added dropwise, water-bath is cooled to 5-25 degree natural subsidence.
After sedimentation, supernatant inspection is packed after qualified.
Example IV: 2.0MLDATHF/ normal heptane/ethylbenzene solution preparation
Under inert gas shielding, by 368 grams of normal heptanes, 12.4 grams of tetrahydrofurans, 13.9 grams of lithiums are placed in 2L there-necked flask, and reaction is mixed
It closes object and is warming up to 30-35 degree, 112 grams of tetrahydrofuran solutions of 104.5 grams of styrene are added dropwise, maintain reaction solution temperature during being added dropwise
Degree is no more than 40 degree.Stop stirring after reacting half an hour after being added dropwise, water-bath is cooled to 5-25 degree natural subsidence.
After sedimentation, supernatant inspection is packed after qualified.
Embodiment five:
Under inert gas shielding, by 368 grams of disopropyl ethyl amines, 12.4 grams of tetrahydrofurans, 13.9 grams of lithiums are placed in 2L there-necked flask,
Reaction mixture is warming up to 30-35 degree, and 112 grams of tetrahydrofuran solutions of 104.5 grams of styrene are added dropwise, and remains anti-during being added dropwise
Liquid temperature is answered to be no more than 40 degree.Stop stirring after reacting half an hour after being added dropwise, water-bath is cooled to 5-25 degree natural subsidence.
After sedimentation, supernatant inspection is packed after qualified.
Embodiment six:
Under inert gas shielding, by 355 grams of dimethylethyl amines, 12.4 grams of tetrahydrofurans, 13.9 grams of lithiums are placed in 2L there-necked flask,
Reaction mixture is warming up to 30-35 degree, and 112 grams of tetrahydrofuran solutions of 104.5 grams of styrene are added dropwise, and remains anti-during being added dropwise
Liquid temperature is answered to be no more than 40 degree.Stop stirring after reacting half an hour after being added dropwise, water-bath is cooled to 5-25 degree natural subsidence.
After sedimentation, supernatant inspection is packed after qualified.
Claims (5)
1. a kind of method for preparing lithium diisopropylamine, which is characterized in that the preparation method the following steps are included:
Step 1: reaction kettle being cleaned up, inert gas replacement three times, sequentially adds raw material, solvent, lithium metal；
Step 2: reaction mixture is warming up to 25-60 DEG C；
Step 3: maintaining 25-60 DEG C of reacting liquid temperature, into step 2 gained mixture, the molten of isoprene or styrene is added dropwise
Liquid starts that a small amount of initiation reaction is added dropwise, and maintains temperature of reaction system after initiation by adjusting rate of addition and circulating water velocity,
It prevents from temperature from crossing high product to degenerate；
Step 4: after being added dropwise, after the reaction was continued 0.5-2 hours, circulating water cooling, natural subsidence, supernatant is LDA phase
The solution answered.
2. a kind of method for preparing lithium diisopropylamine according to claim 1, which is characterized in that preparation method step
Raw materials used and solvent is n-hexane in rapid 2, normal heptane, tetrahydrofuran, methyl tertiary butyl ether(MTBE), ether, disopropyl ethyl amine or
Dimethylethyl amine.
3. a kind of method for preparing lithium diisopropylamine according to claim 1, which is characterized in that preparation method step
Temperature in rapid 2 is 35-40 DEG C.
4. a kind of method for preparing lithium diisopropylamine according to claim 1, which is characterized in that preparation method step
Maintenance temperature in rapid 3 is 35-40 DEG C.
5. a kind of method for preparing lithium diisopropylamine according to claim 1, which is characterized in that preparation method step
The solution solvent of isoprene or styrene is methyl tertiary butyl ether(MTBE) or tetrahydrofuran in rapid 3.
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| CN201711198198.9A CN109836440A (en) | 2017-11-25 | 2017-11-25 | A kind of preparation method of lithium diisopropylamine |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112707929A (en) * | 2020-12-24 | 2021-04-27 | 绍兴上虞华伦化工有限公司 | Process for preparing bis (trimethyl disilyl) lithium amide |
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2017
- 2017-11-25 CN CN201711198198.9A patent/CN109836440A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112707929A (en) * | 2020-12-24 | 2021-04-27 | 绍兴上虞华伦化工有限公司 | Process for preparing bis (trimethyl disilyl) lithium amide |
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Application publication date: 20190604 |